Cationic ring-opening polymerization of 2-propyl-2-oxazolines: Understanding structural effects on polymerization behavior based on molecular modeling

wim — Mon, 10 Jun 2013 13:23:46 +0000

H. Goossens, S. Catak, M. Glassner, V. De La Rosa, B. Monnery, F. De Proft, V. Van Speybroeck, R. Hoogenboom

ACS Macro Letters

2, 651-654

2013

Abstract

The surprising difference in the cationic ring-opening polymerization rate of 2-cyclopropyl-2-oxazoline versus 2-n-propyl-2-oxazoline and 2-isopropyl-2-oxazoline was investigated both experimentally and theoretically. The polymerization kinetics of all three oxazolines were experimentally measured in acetonitrile at 140 °C, and the polymerization rate constant (kp) was found to decrease in the order c-PropOx > n-PropOx > i-PropOx. Theoretical free energy calculations confirmed the trend for kp, and a set of DFT-based reactivity descriptors, electrostatics, and frontier molecular orbitals were studied to detect the factors controlling this peculiar behavior. Our results show that the observed reactivity is dictated by electrostatic effects. More in particular, the charge on the nitrogen atom of the monomer, used to measure its nucleophilicity, was the most negative for c-PropOx. Furthermore, the electrophilicity of the cations does not change substantially, and thus, the nucleophilicity of the monomers is the driving factor for kp.

DOI

http://dx.doi.org/10.1021/mz400293y

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13_ACSMacroLetters_2,651_Goossens.pdf

Cationic ring-opening polymerization of 2-propyl-2-oxazolines: understanding structural effects on polymerization behavior based on molecular modeling

samuel — Thu, 06 Feb 2020 11:22:09 +0000

M. Glassner, H. Goossens, S. Catak, V. De La Rosa, B. Monnery, F. De Proft, V. Van Speybroeck, R. Hoogenboom

ISBN/ISSN:

Talk

Conference / event / venue

248th National Meeting of the American-Chemical-Society (ACS 2014 )

San Francisco, CA

Sunday, 10 August, 2014 to Thursday, 14 August, 2014

Center for Molecular Modeling - M. Glassner

Cationic ring-opening polymerization of 2-propyl-2-oxazolines: Understanding structural effects on polymerization behavior based on molecular modeling

Abstract

DOI

Private attachment

Cationic ring-opening polymerization of 2-propyl-2-oxazolines: understanding structural effects on polymerization behavior based on molecular modeling

Conference / event / venue